Role of Interfacial Defects in Photoelectrochemical Properties of BiVO4 Coated on ZnO Nanodendrites: X-ray Spectroscopic and Microscopic Investigation.

Synchrotron-based X-ray spectroscopic and microscopic techniques are used to identify the origin of enhancement of the photoelectrochemical (PEC) properties of BiVO4 (BVO) that is coated on ZnO nanodendrites (hereafter referred to as BVO/ZnO). The atomic and electronic structures of core-shell BVO/ZnO nanodendrites have been well-characterized, and the heterojunction has been determined to favor the migration of charge carriers under the PEC condition. The variation of charge density between ZnO and BVO in core-shell BVO/ZnO nanodendrites with many unpaired O 2p-derived states at the interface forms interfacial oxygen defects and yields a band gap of approximately 2.6 eV in BVO/ZnO nanocomposites. Atomic structural distortions at the interface of BVO/ZnO nanodendrites, which support the fact that there are many interfacial oxygen defects, affect the O 2p-V 3d hybridization and reduce the crystal field energy 10Dq ∼2.1 eV. Such an interfacial atomic/electronic structure and band gap modulation increase the efficiency of absorption of solar light and electron-hole separation. This study provides evidence that the interfacial oxygen defects act as a trapping center and are critical for the charge transfer, retarding electron-hole recombination, and high absorption of visible light, which can result in favorable PEC properties of a nanostructured core-shell BVO/ZnO heterojunction. Insights into the local atomic and electronic structures of the BVO/ZnO heterojunction support the fabrication of semiconductor heterojunctions with optimal compositions and an optimal interface, which are sought to maximize solar light utilization and the transportation of charge carriers for PEC water splitting and related applications.

Enhancement in thermoelectric properties due to Ag nanoparticles incorporated in Bi2Te3 matrix.

The present study aims to see the enhancement in thermoelectric properties of bismuth telluride (Bi2Te3) annealed at different temperatures (573 and 773 K) through silver (Ag) nano-inclusions (0, 2, 5, 10, 15 and 20 wt %). Transmission electron microscopy (TEM) images of Ag incorporated in Bi2Te3 annealed at 573 K shows tubular, pentagonal, trigonal, circular and hexagonal nanoparticles with sizes of 6-25 nm (for 5 wt % Ag ) and 7-30 nm (for 20 wt % Ag). Ag incorporated in Bi2Te3 annealed at 773 K shows mainly hexagonally shaped structures with particle sizes of 2-20 nm and 40-80 nm (for 5 wt % Ag) and 10-60 nm (for 20 wt % Ag). Interestingly, the samples annealed at 573 K show the highest Seebeck coefficient (S, also called thermopower) at room temperature (p-type behavior) for 5% Ag which is increased ca. five-fold in comparison to Ag-free Bi2Te3, whereas for samples with the same content (5% Ag) annealed at 773 K the increment in thermopower is only about three-fold with a 6.9-fold enhancement of the power factor (S 2σ). The effect of size and shape of the nanoparticles on thermoelectric properties can be understood on the basis of a carrier-filtering effect that results in an increase in thermopower along with a control over the reduction in electrical conductivity to maintain a high power factor yielding a high figure of merit.

Evolution of nanostructured single-phase CoSb3 thin films by low-energy ion beam induced mixing and their thermoelectric performance.

Skutterudites are emerging as potential candidates that show high efficiency and thus provide an ideal platform for research. The properties of nanostructured films of skutterudites are different from those of the corresponding bulk. The present study reports the evolution of nanostructured single-phase CoSb3 fabricated by using low-energy ion irradiation of Co/Sb bilayer films and subsequent annealing at an optimized temperature and their Seebeck coefficients (S). The effects of ion beam parameters with annealing on the phase evolution and nanostructure modifications were studied. An increase in Xe+ ion fluence resulted in complete mixing of Co/Sb on postannealing forming flower-like nanostructures of single phase CoSb3. The temperature-dependent electrical resistivity (ρ) increases with the ion fluence because of defect creation which further increases on postannealing due to surface nanostructuring. The S of these films of CoSb3 is found to be higher and this is attributed to the formation of a uniform layer of nanostructured CoSb3 alloy thin film. The S and Hall coefficients of all these films are negative implying that they are n-type semiconductors.

Robust water repellent ZnO nanorod array by Swift Heavy Ion Irradiation: Effect of Electronic Excitation Induced Local Chemical State Modification.

Tailoring the surface properties by varying the chemistry and roughness could be of interest for self-cleaning applications. We demonstrate the transformation of hydrophobic ZnO Nano rod (NR) array into superhydrophobic nature by changing the local chemical state and without altering the surface roughness by swift heavy ion (SHI) irradiation. The aligned ZnO NR arrays were irradiated using 150 MeV Ag ions with different fluences from 5E10 to 3E12 ions/cm2. The observed static water contact angles of ZnO NRs samples were 103° ± 3°, 152° ± 4°,161° ± 3°, 164° ± 2°, 167° ± 2°,154 ± 3° and 151° ± 2° for the pristine, ion fluencies of 1E11, 3E11, 5E11, 7E11, 1E12 and 3E12 ions cm-2, respectively. The change in local surface chemistry via formation of surface oxygen related defects due to electronic excitations induced by ion irradiation determine the water dewetting properties. It is found that surface oxygen related defects could be tuned by varying the fluence of the SHIs. Durability tests show that the SHI induced surface oxygen-deficient ZnO NRs have the stable superhydrophobic behavior for more than a year.

Synthesis of cobalt nanoparticles on Si (100) by swift heavy ion irradiation.

We report the growth and characterization of uniform-sized nanoparticles of cobalt on n-type silicon (100) substrates by swift heavy ion (SHI) irradiation. The Co thin films of 25-nm thicknesses were grown by e-beam evaporation and irradiated with two different types of ions, 45-MeV Li3+ and 100-MeV O7+ ions with fluences ranging from 1 × 1011 to 1 × 1013 ions/cm2. SHI irradiation, with the beam rastered over the area of the film, resulted in the restructuring of the film into a dense array of Co nanostructures. Surface topography studied by atomic force microscopy revealed narrowed size distributions, with particle sizes ranging from 20 to 50 nm, formed through a self-organized process. Ion fluence-dependent changes in crystallinity of the Co nanostructures were determined by glancing angle X-ray diffraction. Rutherford backscattering spectroscopy analysis showed the absence of beam-induced mixing in this system. Surface restructuring and beam-induced crystallization are the dominant effects, with the nanoparticle size and density being dependent on the ion fluence. Results are analyzed in the context of molecular dynamics calculations of electron-lattice energy transfer.

Nanocomposite ZnO-SnO2 Nanofibers Synthesized by Electrospinning Method.

We report the characterization of mixed oxides nanocomposite nanofibers of (1 - x) ZnO-(x)SnO2 (x ≤ 0.45) synthesized by electrospinning technique. The diameter of calcined nanofibers depends on Sn content. Other phases like SnO, ZnSnO3, and Zn2SnO4 were absent. Photoluminescence studies show that there is a change in the blue/violet luminescence confirming the presence of Sn in Zn-rich composition. Present study shows that the crystalline nanocomposite nanofibers with stoichiometry of (1 - x)ZnO-(x)SnO2 (x ≤ 0.45) stabilize after the calcination and possess some morphological and optical properties that strongly depend on Sn content.

Growth of nanograins in TiO2 nanofibers synthesized by electrospinning.

Present study focuses the effect of calcination temperature and its duration on the morphology and growth of nanograins in individual TiO2 nanofibers synthesized by electrospinning method. Polyvinyl acetate and titanium tetraisopropoxide were used as chemical precursors along with other standard solvents in the synthesis process. This study shows that synthesized TiO2 nanofibers are randomly arranged and spreads uniformly over the Si substrate and possess polycrystalline nature consisting of nanograins. Similar to the sintering behavior generally observed in bulk ceramics, the nanograins coalesce and grow under higher calcination temperature and longer calcination time. The activation energy for the growth of nanograins is found to be 47.2 kJ/mol. The dominant growth mechanism changes depending on the stages of calcination.

Thickness-dependent electronic structure of intermetallic CeCo2 nanothin films studied by X-ray absorption spectroscopy.

We report the electronic structure study of intermetallic CeCo2 nanothin films of various thicknesses by X-ray absorption near-edge structure (XANES) spectroscopy at Ce L3-, Co K-, and L2,3-edges. The Ce L3-edge absorption spectra reveal that the contribution of tetravalent Ce component increases with the film thickness, and all investigated nanothin films exhibit intermediate valence nature. Variation of the spectral intensities observed at the Co K-edge threshold implies modification in the Co 3d states and the enhancement of 3d-4f-5d hybridization. The Co 3d and Ce 4f occupation numbers were estimated from these spectroscopic results. The present study brings out how the surface-to-bulk ratio and the charge transfer between Ce and Co ions affect the electronic structure of nanothin films.

Electronic structure of P-doped ZnO films with p-type conductivity.

The electronic structure of laser-deposited P-doped ZnO films was investigated by X-ray absorption near-edge structure spectroscopy (XANES) at the O K-, Zn K-, and Zn L3-edges. While the O K-edge XANES spectrum of the n-type P-doped ZnO demonstrates that the density of unoccupied states, primarily O 2p-P 3sp hybridized states, is significantly high, the O K-edge XANES spectrum of the p-type P-doped ZnO shows a sharp decrease in intensity of the corresponding feature indicating that P replaces O sites in the ZnO lattice, and thereby generating P(O). This produces holes to maintain charge neutrality that are responsible for the p-type behavior of P-doped ZnO. Both the Zn K-, and Zn L3-edge XANES spectra of the P-doped ZnO reveal that Zn plays no significant role in the p-type behavior of ZnO:P.